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Carboxylic acids make up a well-known group of organic friction modifiers (OFMs). OFMs can present different types of polar heads that can eventually lead to different surface adsorption properties and tribological responses. Therefore, the goal of this work is to study the effects of the polar head type on the frictional and wear performances of carboxylic acids in a water-based lubricant. Lauric acid (C12) was chosen as the reference OFM, and methyl laurate and monolaurin were chosen for the comparison. Sliding friction tests were performed on stainless steel against alumina balls under boundary lubricating conditions. The effect of the adsorbed layers and the tribofilm formation was studied by varying the initial maximum hertzian contact pressure, i.e., tests were performed at 1.97 and 0.66 GPa. At the lowest contact pressure, not enough load is applied to obtain enough plastic deformation on the asperity contacts. In this case, a combination of asperity contacts and a thick fluid film formation results in a lack of tribofilm formation, whereas at the highest contact pressure, tribofilms are formed in the asperity contact through tribochemical reactions. Methyl laurate showed no adsorption on the surface, and it was not tested further. C12 and monolaurin showed good adsorption, but the adsorbed layers had different viscoelastic properties. Micro and macrotribological tests showed good frictional behavior for C12 at 0.5 wt % concentration due to the good viscoelastic properties of its adsorbed layer. The adsorbed layer of monolaurin did not show good friction-reducing ability during the micro tribological tests due to its poorer viscoelastic properties. However, the macro tribological tests revealed that monolaurin forms a robust tribofilm protecting the surface from wear and efficiently reducing friction at a concentration of 0.5 wt % resulting in the lowest wear and friction values as observed in this study.

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In the last years, diamond like carbon (DLC) coatings doped with both carbide forming and non-carbide forming metallic elements have attracted great interest as novel self-lubricating coatings. Due to the inherent properties of DLC, the doping process can provide adsorption sites for lubricant additives depending on the chemical and electrochemical state of the surface. Ionic liquids (ILs) are potential lubricant additives with good thermal stability, non-flammability, high polarity, and negligible volatility. These characteristics make them also ideal for polar fluids, like water-based lubricants. In this work, three different DLC coatings (DLC, W- and Ag-doped DLC) were deposited on stainless steel substrates and their friction in dry and lubricated conditions in water-based lubricants was studied. Three ILs, tributylmethylphosphonium dimethylphosphate (PP), 1,3-dimethylimidazolium dimethylphosphate (IM) and 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate (BMP) were used as additives and compared with a well-known organic friction modifier (dodecanoic acid). The results showed better mechanical integrity, toughness and adhesion of the doped coatings compared to the undoped DLC. The Ag-doped DLC coating had the best mechanical properties of all the coatings. W formed tungsten carbide precipitates in the DLC coating. Two different additive-adsorption mechanisms controlled friction: a triboelectrochemical activation mechanism for Ag-DLC, and an electron-transfer mechanism for W-DLC resulting in the largest reduction in friction.

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Two ionic liquids, tributylmethylphosphonium dimethylphosphate (PP) and 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate (BMP), as lubricant additives in polyalphaolefin (PAO8) were studied under boundary lubricating conditions on two types of steel (AISI 52100 bearing steel and AISI 316L stainless steel). The tribological behavior of these ILs was compared with dodecanoic acid, a well-known organic friction modifier. This study employs a ball-on-disk tribometer with an alumina ball as a counterpart. A range of advanced analytical tools are used to analyze the tribofilms, including scanning electron microscopy equipped with a focused ion beam, scanning transmission electron microscopy equipped with X-ray energy-dispersive spectroscopy, and X-ray photoelectron spectroscopy. A quartz crystal microbalance with dissipation was used to study the surface adsorption of the additives on iron- and stainless steel-coated sensors to reveal the adsorption kinetics, adsorbed layer mass, and bonding strength of the adsorbed layer on the metallic surfaces. The most important factors controlling friction and wear are the thickness and viscoelastic properties of the adsorbed layer, the thickness and chemical composition of the tribofilm, and the hardness and chemical composition of steel. Among all additives studied, BMP on stainless steel gives a strongly adsorbed layer and a durable tribofilm, resulting in low friction and excellent antiwear properties.

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New azo-azomethine sensor, HL, has been synthesized and characterized using standard spectroscopic methods. HL was found to sense CN- and AcO- in DMSO and semi-aqueous media over other anions such as F-, Cl-, Br-, I-, H2PO4- and HSO4-. The anions recognition ability of HL was also evaluated using UV-Vis absorption and 1H NMR spectroscopy. Importantly, HL can detect CN- and AcO- in DMSO even at 0.7 ppm and 1.3 ppm, respectively. The binding stoichiometry between HL and the mentioned anions was found to be 1:1 with binding constants of 8.81 × 103 M-1 and 3.64 × 104 M-1 for CN- and AcO-, respectively. Successfully, HL was used for the detection of sodium diclofenac over the other opiate drugs such as codeine phosphate, noscapine hydrochloride, papaverine hydrochloride, and morphine sulfate. The designed chemosensor has also shown highly promising results for the qualitative and quantitative detection of sodium diclofenac in oral pills.

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Tris(2-(2-formylphenoxy)ethyl)amine was designed and synthesized by reaction of salicylaldehyde with tris(2-chloroethyl)amine hydrochloride and evaluated as a new multi-functional cross-linker for preparation of new pH- and thermo-responsive chitosan hydrogels through formation of covalent Schiff-base linkage. The structure and properties of the hydrogels were characterized by FT-IR, 1H NMR and scanning electron microscopy (SEM). The swelling behavior of prepared hydrogels at different pHs and temperatures was investigated. Also, in vitro controlled release behavior of the metronidazole model drug was studied with prepared hydrogels. The release profiles of metronidazole from the hydrogels were determined by UV-Vis absorption measurement. The results showed that the new hydrogels exhibit a pH and temperature-responsive swelling ratio. Also, the pH and temperature were found to strongly influence the drug release behavior of these swollen polymers. Due to the concurrent rapid and significant stimuli-response, these smart hydrogels prepared from chitosan as a natural polymer may expand the scope of hydrogel applications in various fields of research such as targeted (cellular or tissue) delivery of drugs. In addition, these new hydrogels can be used to improve bioavailability, sustain release of drugs or solubilize drugs for systemic delivery.

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The immobilized azo-azomethine receptors on amorphous SiO2, S-B, SiO2 nanoparticles, S-NPs, and NaY zeolite, S-ZY, have been prepared and applied as solid phase sensors for detection of HSO4-, over other interfering anions, in 100% aqueous media. Remarkably, S-B and S-ZY show unique and rapid sensitivity towards HSO4-, which could it easily visualized through naked eye detection even at 5×10-4molL-1 and 4×10-4molL-1, respectively. The fabricated solid phase sensors were characterized using powder XRD diffraction, TGA-DTA, FE-SEM and also FT-IR techniques. Moreover, the related molecular anion receptor, HL, has been prepared and used for naked eye detection of F- and AcO-, in dry DMSO. The anions recognition ability of HL was also evaluated using UV-Vis and 1H NMR spectroscopic methods.

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Two new azo-azomethine receptors, H2L1 and H2L2, containing hydrazine, naphthalene and different electron withdrawing groups, Cl and NO2, have been designed and synthesized for qualitative and quantitative detection of Cu2+ and Co2+ in aqueous media. The crystal structure of H2L1is reported. The H2L1was used as a chemosensor for selective detection of trace amount of Cu2+ in aqueous media. H2L2 was also applied to naked-eye distinction of Cu2+ and Co2+ from other transition metal ions in aqueous media. Detection limit of Cu2+ is 1.13µM and 1.26µM, in water, for H2L1 and H2L2, respectively, which are lower than the World Health Organization (WHO) recommended level. The binuclear Cu2+ and Co2+ complexes of the receptors have been also prepared and characterized using spectroscopic methods and MALDI-TOF mass analysis. Furthermore, the binding stoichiometry between the receptors upon the addition Cu2+ and Co2+ has been investigated using Job's plot. Moreover, the fluorescence emission spectra of the receptors and their metal complexes are also reported.

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Achieving specific selectivity and high sensitivity for the colorimetric recognition of copper(II) ions in aqueous media over a complex background of potentially competing metal ions is inherently challenging in sensor development. Thus, a novel azo-azomethine receptor (L) based on the combination of 2-amino-3-(5-bromo-2-hydroxybenzylamino)maleonitrile and azo-coupled salicylaldehyde scaffold has been designed and synthesized for the naked-eye and rapid detection of Cu(2+) ion at trace level in a wide pH range. Accordingly, the devised chemosensor distinguished Cu(2+) from other metal ions by distinct color change from light yellow to light brown without any expensive equipment. The binding stoichiometry between Cu(2+) and L has been investigated using Job's plot and MALDI-TOF mass analysis. Remarkably, the current sensor can detect Cu(2+) ions even at 1.07 µM level, which is lower than the World Health Organization (WHO) permissible level (30 µM) in drinking water. Furthermore, sensor L was successfully utilized in the preparation of test strips for the detection of copper(II) ions from aqueous environment.

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New N-monosubstituted diaminomaleonitrile-based azo-azomethine dyes have been synthesized in order to develop colorimetric sensors for detection of biologically important anions in aqueous media. Importantly, the reported sensor decorated with strong electron-withdrawing group can detect inorganic fluoride in water even at 0.037 ppm level, which is lower than WHO permissible level (below 1 ppm). Successfully, the prepared dyes were used for qualitative and quantitative detection of inorganic fluoride in toothpaste and mouthwash. The anion recognition mechanism was also investigated by detailed UV-Vis and (1)H NMR experiments. The detailed (1)H NMR experiments corroborated that anion recognition is based on the deprotonation phenomenon.

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A new chromogenic azo-azomethine sensor, containing active phenolic sites, has been designed and synthesized via condensation reaction of N,N,N',N'-tetrakis(2-aminoethyl)-2,2-dimethyl propane-1,3-diamine with 1-(3-formyl-4-hydroxyphenylazo)-4-nitrobenzene. The anion recognition ability of the synthesized receptor was evaluated using UV-Vis spectroscopy and (1)H NMR technique. The anion recognition studies exhibited that the receptor acts as a sensor for biologically important anions such as F(-), AcO(-) and H2PO4(-) over other anions. The binding stoichiometry between sensor and anions was found to be 1:2. (1)H NMR experiment revealed that sensor recognizes anions via H-bonds and subsequent deprotonation to elicit a vivid color change. Interestingly, the sensory system not only let for the naked eye detection without any spectroscopic instrumentation but also helped to discriminate between anions.

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A new 1,2,4-triazole-based azo-azomethine compound, H2L, has been prepared by condensation reaction of 1-(3-formyl-4-hydroxyphenylazo)-4-ethylbenzene with prepared triazole-based diamine. The structure of H2L was characterized by using FT-IR, UV-Vis and (1)H NMR spectroscopic methods as well as elemental analysis. Hard model chemometrics method has been used to determine the formation constants of zinc(II), copper(II), nickel(II) and cobalt(II) complexes of H2L in DMSO by UV-Vis spectrophotometric method. Solvatochromic behavior of the dye has been also investigated in some organic solvents with different polarities. Thermal properties of the prepared dye was examined by thermogravimetric analysis. Results indicated that the framework of the dye was stable up to 245 °C. Furthermore,(1)H chemical shifts and UV-Vis of H2L were studied by the gauge independent atomic orbital (GIAO), continuous set of gauge transformations (CSGT) and time-dependent density functional theory (TD-DFT) methods respectively at the level of density functional theory using B3LYP/6-311+G(d) basis sets in DMSO. The computational data are in reasonably good agreement with the experimental data.

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A new 1,2,4-triazole-based Schiff base hydrazone with N, O, S donor set of atoms, H(4)L, has been prepared by condensation reaction of N,N'-bis(3-formyl-5-methylsalicylidene)ethane-1,2-diamine, H(2)L, with 4-amino-3-(4-pyridyl)-5-mercapto-1,2,4-triazole. The structure of H(4)L was characterized by using FT-IR, UV-Vis and (1)H NMR spectroscopic methods as well as elemental analysis data. The formation constants of copper(II), cadmium(II), mercury(II) and silver(I) complexes of H(4)L in DMSO were calculated using a hard model chemometrics method applying the spectrophotometric data. The protonation constants of H(4)L were also measured in DMSO-water (1:10) mixture. Furthermore, (1)H chemical shifts of H(4)L were studied by the gauge independent atomic orbital (GIAO) and continuous set of gauge transformations (CSGTs) methods at the level of density functional theory using B3LYP/6-311++G(*) basis sets in gas phase. The computed chemical shifts are in reasonably good agreement with the experimental data.

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Six new water insoluble azo-azomethine dyes have been synthesized via condensation reaction of α,α'-bis(o-aminophenylthio)-1,2-xylene with substituted azo-coupled salicylaldehyde. The condensation reaction provides the expected bis-iminated azo-azomethine dyes in good yields, ranging from 59% to 90%. The dyes have been characterized by IR, UV-Vis and (1)H NMR spectroscopic methods as well as elemental analysis. The thermal behavior of the prepared dyes has been determined using thermogravimetry technique. Furthermore, the effect of various organic solvents with different polarities on the UV-Vis spectra of the dyes has been also studied.

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A new series of monoiminated 1,2,4-triazole-based azo-azomethine dyes have been synthesized via condensation reaction of 4-amino-3-methyl-5-mercapto-1,2,4-triazole with various substituted azo-coupled salicylaldehyde. The dyes have been characterized by using FT-IR, UV-Vis and (1)H NMR spectroscopic methods as well as elemental analysis. The electrochemical behavior of the dyes has been investigated by cyclic voltammetry in DMSO at five different scan rates. Solvatochromic behavior of the dyes has been also investigated in four organic solvents with different polarities. Furthermore, the (1)H chemical shielding of the dyes were studied by the gauge independent atomic orbital (GIAO) method at the level of density functional theory (DFT).

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Four new 1,2,4-triazole-based azo-azomethine dyes were synthesized via condensation of 3,5-diamino-1,2,4-triazole with azo-coupled o-vanillin precursors. The prepared dyes were characterized by IR, UV-vis and (1)H NMR spectroscopic methods as well as elemental analyses. Thermal properties of the prepared dyes were examined by thermogravimetric analysis. Results indicated that the framework of the dyes was stable up to 225 °C. Also, the influence of various factors including time and mixed DMSO/EtOH solution on UV-vis spectra of the dyes were investigated.

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A new asymmetric heptaaza Schiff base macrocyclic bis(pendant donor) manganese(II) complex, [MnL(1)](ClO(4))(2).CH(3)CN (1), has been prepared and characterized by X-ray diffraction and spectroscopic methods. The antimicrobial activity of 1 and a series of its familiar symmetric heptaaza [15]pydieneN(5), [16]pydieneN(5), and [17]pydieneN(5)-based bis-(2-aminoethyl) pendant armed Schiff base macrocyclic complexes of Mn(II) were tested against Escherichia coli, Staphylococcus aureus and Candida albicans. The results showed that the symmetric heptaaza [16]pydieneN(5), and [17]pydieneN(5)-based Schiff base macrocyclic complexes of Mn(II) had remarkable inhibition zone on the culture of S. aureus and E. coli as compared with standard drugs. The optimized geometry of the prepared complex has been obtained from density functional method, DFT, using B3LYP/6-31G* basis set.

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Six pyridazine-based Schiff base ligands, H(2)L(n) (n=1-5) and H(4)L, with N(4)O(2)S(2) and N(4)O(4)S(2) donor set atoms, respectively, were prepared by condensation reaction of 3,6-bis-((2-aminoethyl)thio)pyridazine with various salicyladehyde derivatives in ethanol and under solvent-free polyphosphate ester catalyzed conditions. The acid-base properties of H(2)L(2) and H(2)L(3) in DMSO/water (1:1) solution have been studied by spectrophotometric method at 25 degrees C. Optimized geometries of all compounds were also obtained at the B3LYP level of theory. Additionally, the (13)C chemical shielding of gas phase H(2)L(1) and H(2)L(2) were studied by the gauge independent atomic orbital (GIAO) and continuous set of gauge transformations (CSGT) methods at the level of density functional theory (DFT). The 6-311++G* basis set was utilized for all of the atoms.

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The oxidation of the recently synthesized Schiff base 3,6-bis((2-aminoethyl-5-Br-salicyliden)thio)pyridazine (PABST) with hydrogen peroxide was investigated using spectrophotometric studies. The reaction rate order and observed rate constant of the oxidation reaction was obtained in the mixture of N,N-dimethylformamide (DMF):water (30:70, v/v) at pH 10 using multivariate cure resolution alternative least squares (MCR-ALS) method and rank annihilation factor analysis (RAFA). The effective parameters on the oxidation rate constant such as percents of DMF, the effect of transition metals like Cu(2+), Zn(2+), Mn(2+) and Hg(2+) and the presence of surfactants were investigated. The keto-enol equilibria in DMF:water (30:70, v/v) solution at pH 7.6 was also investigated in the presence of surfactants. At concentrations above critical micelle concentration (cmc) of cationic surfactant cetyltrimethylammonium bromide (CTAB), the keto form was the predominant species, while at concentrations above cmc of anionic surfactant sodium dodecyl sulfate (SDS), the enol form was the predominant species. The kinetic reaction order and the rate constant of tautomerization in micellar medium were obtained using MCR-ALS and RAFA. The results obtained by both the methods were in a good agreement with each other. Also the effect of different volume percents of DMF on the rate constant of tautomerization was investigated. The neutral surfactant (Triton X-100) had no effect on tautomerization equilibrium.

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The equilibria of a new Schiff base derived from 3,6-bis((aminoethyl)thio)pyridazine were studied spectrophotometrically with the aid of factor-analytical methods. Hard modeling program was used for determination of the acidity constants of the Schiff base in dimethylformamide (DMF)/water mixture (30:70 v/v). In this method acidity constant equations act as hard models and the score vectors obtained by decomposing of absorbance data matrix will be linear combinations of equilibrium concentrations of species that exist in the absorption matrix. Two rank annihilation factor analysis (TRAFA) was used as a standard method to investigate the accuracy of the method. The tautomerization constant, K(t), of the Schiff base solution in various DMF/water mixtures has also been determined using spectral variations of the Schiff base solutions in various volume ratios of water with the aid of evolving factor analysis (EFA) and multivariate curve resolution alternative least squares (MCR-ALS) methods. In addition the intramolecular hydrogen bonding strength and its related thermodynamic parameters have been determined using MCR-ALS and spectral variation of the Schiff base solutions in different temperatures.

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New complexes of Co(2+), Ni(2+), Cu(2+) and Zn(2+) with a recently synthesized Schiff base derived from 3,6-bis((aminoethyl)thio)pyridazine were applied for their simultaneous determination with artificial neural networks. The analytical data show the ratio of metal to ligand in all metal complexes is 1:1. The absorption spectra were evaluated with respect to Schiff base concentration, pH and time of the color formation reactions. It was found that at pH 10.0 and 60min after mixing, the complexation reactions are completed and the colored complexes exhibited absorption bands in the wavelength range 300-500nm. Spectral data was reduced using principal component analysis and subjected to artificial neural networks. The data obtained from synthetic mixtures of four metal ions were processed by principal component-feed forward neural networks (PCFFNNs) and principal component-radial basis function networks (PCRBFNs). Performances of the proposed methods were tested with regard to root mean square errors of prediction (RMSEP%), using synthetic solutions. Under the working conditions, the proposed methods were successfully applied to simultaneous determination of Co(2+), Ni(2+), Cu(2+) and Zn(2+) in different vegetable, foodstuff and pharmaceutical product samples.

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